Production of alicyclic (meth)allyl esters for plastic lens compositions

ABSTRACT

An alicyclic (meth)allyl ester monomer obtained by a specific production process. An alicyclic (meth)allyl ester compound for plastic lenses, which can be obtained by a simple and easy production process and which can endure a long-term storages, is produced using the monomer, and a plastic lens is obtained using the compound.

CROSS-REFERENCE TO RELATED APPLICATION

This application is an application filed under 35 U.S.C. §111(a)claiming benefit pursuant to 35 U.S.C. §119(e)(1) of the filing date ofthe Provisional Application No. 60/221,209 filed Jul. 27, 2000, pursuantto 35 §111(b).

TECHNICAL FIELD

The present invention relates to a process for producing a (meth)allylester monomer having an alicyclic structure within the molecule(hereinafter simply referred to as an “alicyclic (meth)allyl estermonomer”) by transesterification of an alkyl ester of a polybasic acidhaving an alicyclic structure with a (meth)allyl ester, a process forproducing an alicyclic (meth)allyl ester compound using an alicyclic(meth)allyl ester monomer produced by the above-described process and apolyhydric alcohol as starting materials, and an alicyclic (meth)allylester compound produced by this process.

The present invention also relates to a plastic lens compositioncontaining the above-described alicyclic (meth)allyl ester compound, aplastic lens obtained by curing the composition, and a process forproducing the plastic lens.

Still further, the present invention relates to a plastic lenscomposition comprising an alicyclic (meth)allyl ester compound, whichcan be used to produce a plastic lens while inhibiting generation ofuneven dyeing and at the same time, preventing a mold from beingdamaged; a plastic lens obtained by curing the composition; and aprocess for producing the plastic lens.

The term “(meth)allyl alcohol” as used herein refers to an allylalcohol, a methallyl alcohol and/or a mixture thereof. The term“(meth)allyl ester monomer” as used herein refers to an allyl estermonomer, a methallyl ester monomer and/or a mixture thereof. The term“(meth)allyl ester compound” as used herein refers to an allyl estercompound, a methallyl ester compound and/or a mixture thereof.

BACKGROUND ART

The alicyclic (meth)allyl ester monomer produced by reacting an alkylester of a polybasic acid having an alicyclic structure with an allylalcohol or a methallyl alcohol is a highly reactive monomer. Thismonomer is used with various crosslinking agents or reactive dilutingagents and the polymer of the monomer itself is widely used for variousmolded articles, laminates, decorative sheets and the like because ofits excellent electrical properties, dimensional stability, heatresistance, weather resistance, chemical resistance and mechanicalproperties. In recent years, the polymer has also been found to haveexcellent optical properties and the use thereof as an optical materialhas begun.

The polyethylene glycol bis(allyl carbonate) resin which has beenheretofore used is low in its polymerization reaction rate as comparedwith the acrylic resin, therefore, the polymerization reaction thereofis easy to control. As a result, a uniform polymerization reaction canbe attained and the plastic lens derived from the polyethylene glycolbis(allyl carbonate) resin is advantageously small in the opticalstrain.

With respect to the dyeability of a plastic lens derived from thepolyethylene glycol bis(allyl carbonate) resin, in the case where aplastic lens obtained by cast molding is dyed by the general means ofdipping the lens in a dye bath at a high temperature, the dyeing densityis known to be excellent as compared with plastic lenses derived fromother resins.

However, the polydiethylene glycol bis(allyl carbonate) resin has aproblem in that when a plastic lens derived from the resin is dyed,uneven dyeing is generated.

In order to overcome this problem, International Patent Publication Nos.WO99/17137 and WO99/38899 discloses use of an allyl ester compoundcontaining a polycarboxylate structure having an alicyclic structure. Inthese publications, it is stated that uniform dyeing, which is requiredfor the dyeability of plastic lens, can be attained, namely, an improvedeffect is provided on the reduction of uneven dyeing.

However, depending on the production process of an allyl ester monomeras a starting material, the above-described allyl ester compoundsometimes fails in satisfying the requirement for long-term storagestability of the composition for optical materials represented by alens.

Known examples of the production process for this kind of allyl estermonomer or methallyl ester monomer include:

1) a synthesis method starting from carboxylic acid chloride and analcohol;

2) a synthesis method starting from an alkali salt of carboxylic acidand an alkyl halide; and

3) a synthesis method starting from carboxylic acid and an alcohol.

However, use of these methods in the production of compounds related tothe present invention has a problem in that in the method 1), the acidchloride as a starting material is expensive.

In the case of applying the method 2), a side reaction of hydrolyzingthe alkyl halide into a (meth)allyl alcohol takes place in a fairly highratio and the operation of separating or recovering the startingmaterials and the by-product is disadvantageously complicated andcostly.

In the method 3), a strong acid catalyst is generally used but the(meth)allyl alcohol is not stable to an acid catalyst usually used andhas a problem in that di(meth)allyl ether is produced as a by-product.In addition to the low yield of (meth)allyl alcohol, it has been foundthat when sulfuric acid or p-toluenesulfonic acid is used as a catalyst,a corresponding allyl ester is produced as the by-product of thecatalyst and these allyl sulfonate esters are difficult to separate fromthe objective alicyclic (meth)allyl ester monomer and in turn, theproduct is relatively low in the stability during a long-term storageand cannot cope with the use where the product is required to have along-term storage stability, such as a composition for optical materialuse.

In this specification, the term “di(meth)allyl ether” refers to adiallyl ether, a dimethallyl ether and/or a mixture thereof.

DISCLOSURE OF INVENTION

By taking account of these problems in conventional techniques, it is anobject of the present invention to provide a process for producing analicyclic (meth)allyl ester monomer, comprising reacting an alkyl esterof a polybasic acid having an alicyclic structure, which has heretoforenot been used as a starting material of the alicyclic (meth)allyl estermonomer, with a (meth)allyl alcohol in the presence of atransesterification catalyst, a process for producing an alicyclic(meth)allyl ester compound having a (meth)allyl ester group at theterminal, using the alicyclic (meth)allyl ester monomer, and thealicyclic (meth)allyl ester compound.

It is another object of the present invention to provide a plastic lenscomposition comprising the alicyclic (meth)allyl ester compound, whichis suitable for the production of optical materials, particularly, aplastic lens, a plastic lens obtained by curing the plastic lenscomposition, and a process for producing the plastic lens.

As a result of extensive investigations to solve the above-describedproblems, the present inventors have found that, when a lower aliphaticalkyl ester of a polybasic acid having an alicyclic structure and a(meth)allyl alcohol are reacted by transesterification while distillingout a lower aliphatic alcohol, the objective alicyclic (meth)allyl estermonomer can be produced. Furthermore, it has been found that analicyclic (meth)allyl ester compound having a (meth)allyl ester group atthe molecular terminal can be produced using the alicyclic (meth)allylester monomer by a transesterification reaction with a polyhydricalcohol and also that this alicyclic (meth)allyl ester compound can besuitably used for optical use. The present invention has beenaccomplished based on these findings.

More specifically, the present invention (I) is a process for producingan alicyclic (meth)allyl ester monomer, comprising reacting an alkylester of a polybasic acid having an alicyclic structure with an allylalcohol and/or a methallyl alcohol in the presence of atransesterification catalyst.

The present invention (II) is a process for producing an alicyclic(meth)allyl ester compound having a terminal structure of formula (1)and a repeating unit of formula (2), comprising transesterifying analicyclic (meth)allyl ester monomer produced by the present invention(I) with a polyhydric alcohol in the presence of a catalyst. The presentinvention (II) includes an alicyclic (meth)allyl ester compound having aterminal structure of formula (1) and a repeating unit of formula (2),which is produced by the production process.

wherein each R¹ independently represents an allyl group or a methallylgroup, each X independently represents an organic residue derived from apolyvalent carboxylic acid having an alicyclic structure, and each Yindependently represents an organic residue derived from a polyhydricalcohol having from 2 to 20 carbon atoms and containing from 2 to 6hydroxyl groups, provided that, by the ester bonding, X may have abranched structure having a terminal group of formula (1) and arepeating unit of formula (2) or may have R¹, and that by the esterbonding, Y may have a branched structure having a terminal group offormula (1) and a repeating unit of formula (2).

The present invention ,(III) is a plastic lens composition comprising analicyclic (meth)allyl ester compound of the present invention (II).

The present invention (IV) is a plastic lens composition comprising atleast one radical polymerization initiator in an amount of 0.1 to 10parts by mass per 100 parts by mass of the entire curable componentcontained in the plastic lens composition.

The present invention (V) is a plastic resin obtained by curing theplastic lens composition of the present invention (III) or (IV).

The present invention (VI) is a process for producing the plastic lensof the present invention (V).

BRIEF DESCRIPTION OF DRAWINGS

The following figures are each a 400 MHz ¹H-NMR spectrum chart of analicyclic allyl ester compound described in the examples.

FIG. 1 is a 400 MHz ¹H-NMR spectrum chart of an alicyclic allyl estercompound obtained in Example 29.

FIG. 2 is a 400 MHz ¹H-NMR spectrum chart of an alicyclic allyl estercompound obtained in Comparative Example 1.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described in detail below.

The present invention (I) which is a process for producing an alicyclic(meth)allyl ester monomer is described below.

The ester of polybasic acid having an alicyclic structure for use in thepresent invention (I) is preferably a dicarboxylic acid ester,tricarboxylic acid ester or tetracarboxylic acid ester of a 5-, 6- or7-membered cycloalkane which may have some other substituents. Examplesthereof include diesters of 1,4-cyclohexanedicarboxylic acid, diestersof 1,3-cyclohexanedicarboxyic acid, triesters of1,2,4-cyclohexanetricarboxylic acid, tetraesters of1,2,4,5-cyclohexanetetracarboxylic acid, diesters of alkyl-substitutedcyclohexane-1,4-dicarboxylic acid and diesters of halogen-substitutedcyclohexane-1,4-dicarboxylic acid.

The term “alkyl” as used herein means an alkyl group having from 1 to 10carbon atoms, which may have a branch, and specific examples thereofinclude a methyl group, an ethyl group, an n-propyl group, an iso-propylgroup, an n-butyl group and a tert-butyl group. Specific examples of the“halogen” include chlorine, bromine and iodine.

Among those, on taking account of the reactivity, preferred are diestersof 1,4-cyclohexanedicarboxylic acid, diesters of1,3-cyclohexanedicarboxylic acid, diesters of 5-alkyl-substitutedcyclohexane-1,4-dicarboxylic acid and diesters of 5-halogen-substitutedcyclohexane-1,4-dicarboxylic acid, more preferred are diesters of1,4-cyclohexanedicarboxylic acid and diesters of1,3-cyclohexanedicarboxylic acid.

The ester component in the polybasic acid ester having an alicyclicstructure for use in the present invention (I) is not particularlylimited as long as it has a group capable of transesterification.Specific examples thereof include a methyl group, an ethyl group, anisopropyl group, an n-propyl group, an isobutyl group, a sec-butylgroup, a tert-butyl group and an n-butyl group. Among these, since thealcohol produced by the transesterification with a (meth)allyl alcoholis preferred to have a boiling point lower than that of the (meth)allylalcohol, a methyl group, an ethyl group and an isopropyl group arepreferred.

The term “alicyclic (meth)allyl ester monomer” as used herein refers to,as described above, a monomer which has an alicyclic structure withinthe molecule and at the same time, in which the carboxylic acid groupdirectly bonded to the alicyclic structure has an ester structure basedon the structure derived from the (meth)allyl alcohol.

Specific examples thereof include diallyl 1,4-cyclohexanedicarboxylate,dimethallyl 1,4-cyclohexanedicarboxylate, allylmethallyl1,4-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate,dimethallyl 1,3-cyclohexanedicarboxylate, allylmethallyl1,3-cyclohexanedicarboxylate, triallyl 1,2,4-cyclohexanetricarboxylate,trimethallyl 1,2,4-cyclohexkanetricarboxylate, allyldimethallyl1,2,4-cyclohexanetricarboxylate, diallylmethallyl1,2,4-cyclohexanetricarboxylate, tetrallyl1,2,4,5-cyclohexanetetracarboylate, triallylmethallyl1,2,4,5-cyclohexanetetracarboxylate, diallyldimethallyl1,2,4,5-cyclohexanetetracarboxylate, allyltrimethallyl1,2,4,5-cyclohexanetetracarboxylate, tetramethallyl1,2,4,5-cyclohexanetetracarboxylate, diallyl 5-alkyl-substitutedcyclohexane-1,4-dicarboxylate, allylmethallyl 5-alkyl-substitutedcyclohexane-1,4-dicarboxylate, dimethallyl 5-alkyl-substitutedcyclohexane-1,4-dicarboxylate, diallyl 5-halogen-substitutedcyclohexane-1,4-dicarboxylate, allylmethallyl 5-halogen-substitutedcyclohexane-1,4-dicarboxylate and dimethallyl 5-halogen substitutedcyclohexane-1,4 -dicarboxylate.

The transesterification catalyst for use in the present invention (I)may, fundamentally, be any catalyst as long as it can activate the estergroup and cause a reaction with an alcohol. Examples thereof include:

alkali metal elements, and oxides, weak acid salts, alcoholates andhydroxides thereof;

alkaline earth metal elements, and oxides, weak acid salts, alcoholatesand hydroxides thereof;

Hf, Mn, U, Zn, Cd, Zr, Pb, Ti, Co and Sn elements, and oxides,hydroxides, inorganic acid salts, alkoxides, organic acid salts andorganic metal complexes thereof;

organic metal compounds including organic tin compounds such asdibutyltin oxide, dioctyltin oxide and dibutyltin dichloride, andorganic titanium compounds such as tetraalkyl titanates, e.g.,tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate;and

tertiary amines such as dimethylaniline and1,4-diazabicyclo[2.2.2]octane.

Among these, preferred are:

a combination of an alkali metal salt of organic acid and/or inorganicacid with a hydroxide and/or an oxide of alkaline earth metal;

organic tin compounds such as dibutyltin oxide, dioctyltin oxide anddibutyltin dichloride;

tetraalkyl titanates such as tetramethyl titanate, tetraisopropyltitanate and tetrabutyl titanate;

alkali metal salts and alkaline earth metal salts of carbonic acid, suchas potassium carbonate and calcium carbonate;

alkyl alkoxides of an alkali metal, such as potassium methoxide, sodiummethoxide, potassium ethoxide and potassium tert-butoxide;

tertiary amines such as dimethylaniline and1,4-diazabicyclo[2.2.2]octane; and

organic metal complexes of hafnium, such as hafnium acetylacetonate.These may be used in a combination of two or more thereof.

In particular, the combination of an alkali metal salt of organic acidand/or inorganic acid with a hydroxide and/or an oxide of alkaline earthmetal is preferred, on taking account of production in industry, becausethe catalyst components precipitate after the completion of reaction andthe product and the catalyst can be separated by only the filtration.

Specific examples of the hydroxide and the oxide of alkaline earth metalused as a catalyst include calcium hydroxide, magnesium hydroxide,barium hydroxide, calcium oxide and magnesium oxide. Among these,calcium hydroxide and calcium oxide are preferred in view of thecapability.

Specific examples of the alkali metal salt of inorganic acid or organicacid present together include sodium acetate, potassium a cetate,lithium acetate, rubidium acetate, cesium acetate, potassium chloride,sodium chloride, sodium sulfate, potassium sulfate, potassium carbonate,sodium carbonate, lithium carbonate, rubidium carbonate, potassiumphosphate, potassium nitrate, sodium hydrogencarbonate and cesiumcarbonate. Among these, potassium acetate, sodium acetate, rubidiumacetate and cesium acetate are preferred in view of their capability.

Among the combinations of an alkali metal salt of organic acid and/orinorganic acid with a hydroxide and/or an oxide of alkaline earth metal,preferred are a combination of calcium hydroxide and cesium acetate, acombination of calcium oxide and cesium acetate, a combination ofcalcium hydroxide and rubidium acetate, a combination of calciumhydroxide and potassium acetate, a combination of calcium oxide andpotassium acetate, a combination of calcium hydroxide and sodium acetateand a combination of calcium oxide and sodium acetate, and morepreferred are a combination of calcium hydroxide and cesium acetate, acombination of calcium hydroxide and potassium acetate, a combination ofcalcium hydroxide and rubidium acetate and a combination of calciumoxide and potassium acetate.

With respect to the use ratio, the alkali metal salt of organic acidand/or inorganic acid is preferably used in an amount of 0.001 to 1 partby mass, more preferably from 0.01 to 0.5 part by mass, per 1 part bymass of the hydroxide and/or oxide of alkaline earth metal.

If the ratio of the alkali metal salt of organic acid and/or inorganicacid to the hydroxide and/or oxide of alkaline earth metal is less thanthis range, the reaction disadvantageously takes a long time, whereas ifit exceeds this range, the reaction solution may be seriously coloredand this is not preferred.

The reaction form used is a method of heating a polyvalent ester ofpolybasic acid having an alicyclic structure with a (meth)allyl alcoholin the presence of a catalyst. The reaction is preferably performed at atemperature of 30 to 200° C., more preferably from 50 to 150° C., underatmospheric pressure or applied pressure or if desired, under reducedpressure in an inert gas atmosphere. In order to more effectivelyperform the reaction, it is preferred to swiftly distill off thealcohols produced by the reaction scheme.

The (meth)allyl alcohol must be used at least in a theoretical amount tothe starting material ester and on considering the reaction rate,equilibrium and the like, the (meth)allyl alcohol is preferably used inexcess mol. However, if the (meth)allyl alcohol is used too excessively,an effect counterbalancing the excess amount is not brought out and thisis not preferred in view of the profitability. Accordingly, the(meth)allyl alcohol is used in an amount of 1.2 to 10 times in mol, morepreferably from 1.5 to 4 times in mol, based on the theoretical amountto the starting material ester. The starting material ester and the(meth)allyl alcohol may be charged at the beginning of the reaction ormay be sequentially added on the way of the reaction.

The amount of the catalyst used is from 0.01 to 2% by mass, preferablyon the order of 0.1 to 1% by mass. If the amount used is too small, thereaction rate decreases, whereas if the amount used exceeds theabove-describe range, not only an effect counterbalancing the amountcannot be obtained but also serious coloration takes place or the yieldrather decreases due to the side reaction. Moreover, the use in excessincurs a problem that the separation from the catalyst requiresconsiderable time and labor.

The method for isolating the alicyclic (meth)allyl ester monomerproduced in the reaction system of the present invention is prominentlycharacterized in that when the above-described mixed catalyst is used, apurified product usable as a product can be obtained only by separatingthe catalyst using appropriate means such as filtration after the(meth)allyl alcohol is distilled off, and then subjecting the residue toacid washing and alkali washing.

Even in the case of using other catalysts, by purifying the reactionproduct using appropriate means such as distillation, a high-qualityproduct can be obtained.

The present invention (II) is described below. The present invention(II) is a process for producing an alicyclic (meth)allyl ester compoundhaving a terminal structure of formula (1) an d a repeating unit offormula (2), comprising transesterifying an alicyclic (meth)allyl estermonomer produced by the present invention (I) with a polyhydric alcoholin the presence of a catalyst. The present invention (II) includes analicyclic (meth)allyl ester compound having a terminal structure offormula (1) and a repeating unit of formula (2), which is produced bythis production process.

wherein each R¹ independently represents an allyl group or a methallylgroup, each X independently represents an organic residue derived from apolyvalent carboxylic acid having an alicyclic structure, and each Yindependently represents an organic residue derived from a polyhydricalcohol having from 2 to 20 carbon atoms and containing from 2 to 6hydroxyl groups, provided that, by the ester bonding, X may have abranched structure having a terminal group of formula (1) and arepeating unit of formula (2) or may have R¹, and that by the esterbonding, Y may have a branched structure having a terminal group offormula (1) and a repeating unit of formula (2).

The alicyclic allyl ester compound having a terminal structure offormula (1) and a repeating unit of formula (2) for use in the presentinvention can be produced by transesterifying a (meth)allyl esterproduced by the present invention (I) with a polyhydric alcohol in thepresence of a catalyst.

The catalyst for use in the production step of the alicyclic allyl estercompound having a terminal structure of formula (1) and a repeating unitof formula (2) is not particularly limited as long as it is a catalystwhich can be generally used in transesterification. An organic metalcompound is preferred and specific examples thereof includetetraisopropoxy titanium, tetra-n-butoxy titanium, dibutyltin oxide,dioctyltin oxide, hafnium acetylacetonate and zirconium acetylacetonate,however, the present invention is not limited thereto. Among these,dibutyltin oxide and dioctyltin oxide are preferred.

The reaction temperature in this production step is not particularlylimited, however, the reaction temperature is preferably from 100 to230° C., more preferably from 120 to 200° C. In the case of using asolvent, the reaction temperature is sometimes limited by the boilingpoint of the solvent.

In this production step, a solvent is usually not used, however, asolvent may be used, if desired. The solvent which can be used is notparticularly limited as long as it does not inhibit thetransesterification. Specific examples thereof include benzene, toluene,xylene and cyclohexane, but the present invention is not limitedthereto. Among these, benzene and toluene are preferred. However, asdescribed above, this production step can also be performed withoutusing a solvent.

The alicyclic allyl ester compound having a terminal structure offormula (1) and a repeating unit of formula (2), which is produced bythe above-described production process, is described below.

In formula (1), each R¹ independently represents an allyl or methallylgroup. In formula (1) or (2), each X independently represents an organicresidue derived from a polyvalent carboxylic acid having an alicyclicstructure.

The term “each R¹ independently represents an allyl group or a methallylgroup” as used herein means that the terminal groups represented byformula (1) all may be an allyl group, all may be a methallyl group,partly may be allyl group or partly may be a methallyl group.

The term “each X independently represents” as used herein means that inthe following structural formula (3) as one example of the repeatingunit represented by formula (1) or (2), the Xs contained in therepeating structure are independent of each other.

This is described below by referring to, for example, structural formula(3) showing the case where Y is an organic residue derived from ethyleneglycol:

wherein each X independently represents an organic residue derived froma polyvalent carboxylic acid having an alicyclic structure and qrepresents 0 or an integer of 1 or more.

In structural formula (3), the Xs in the number of (q+1) may be organicresidues all derived from polyvalent carboxylic acids having differentalicyclic structures (namely, organic residues are derived one by onefrom polyvalent carboxylic acids having (q+1) kinds of alicyclicstructures) or may be organic resides all derived from polyvalentcarboxylic acids having the same alicyclic structure (namely, organicresidues in the number of (q+1) derived from polyvalent carboxylic acidshaving one kind of alicyclic structure). A mixed structure may also beformed, where, out of the organic residues in the number of (q+1), someorganic residues are derived from polyvalent carboxylic acids having thesame alicyclic structure and some others are derived from polyvalentcarboxylic acids having different kinds of alicyclic structures.Furthermore, the mixed structure may be completely random throughout thestructure or, in the mixed structure, a part may be repeated.

When a part or all of Xs are an organic residue having three or morecarboxyl groups and being derived from a polyvalent carboxylic acidhaving an alicyclic structure, a part or all of the Xs may have abranched structure having a terminal group of formula (1) and arepeating unit of formula (12) or may have R¹, through an ester bond.More specifically, when an organic residue derived fromcyclohexane-1,2,4-tricarboxylic acid, as one example of the organicresidue derived from a trivalent or greater valent carboxylic acidhaving an alicyclic structure, is present in the Xs, the alicyclic allylester compound as the present invention (II) having a terminal structureof formula (1) and a repeating unit of formula (2) may have a partialstructure represented by the following structural formula (4):

wherein each Y independently represents an organic residue derived froma polyhydric alcohol having from 2 to 20 carbon atoms and containingfrom 2 to 6 hydroxyl groups.

Of course, even when a part or all of the Xs are an organic residuederived from a polyvalent carboxylic acid having 3 or more carboxylgroups and having an alicyclic structure, each X may not have a branchedstructure at all.

The carboxylic groups may be retained as such. In particular, in thecase where a part or all of the Xs is an organic residue derived from apolyvalent carboxylic acid having 3 or more carboxylic groups and havingno branched structure, the carboxyl group in the moiety having nobranched structure may be retained as such, but the alicyclic(meth)allyl ester compound of the present invention (II) may alsoinclude such a compound.

In formula (1) or (2), each X independently represents an organicresidue derived from a polyvalent carboxylic acid having an alicyclicstructure.

Specific examples of the “polyvalent carboxylic acid having an alicyclicstructure”, as used herein, include 1,2-cyclohexanedicarboxyliclacid,1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,4-methyl-cyclohexane-1,2-dicarboxylic acid,3-methyl-cyclohexane-1,2-dicarboxylic acid and1,2,4-cyclohexanetricarboxylic acid. Needless to say, the presentinvention is not limited thereto and these acids may be usedindividually or in combination of two or more thereof.

Among these polyvalent carboxylic acids having an alicyclic structure,in view of the flowability and transesterification property of thealicyclic allyl ester compound having a terminal structure of formula(1) and a repeating unit of formula (2), preferred are1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarbxoylic acid, 4-methyl-cyclohexane-1,2-dicarboxylicacid, 3-methyl-cyclohexane-1,2-dicarboxylic acid and a mixture of two ormore thereof, more preferred are 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid and a mixture thereof.

In formula (2), each Y independently represents an organic residuederived from a polyhydric alcohol having from 2 to 20 carbon atoms andcontaining from 2 to 6 hyroxyl groups.

The term “each Y independently represents” as used herein means that inthe following formula (5) as one example of the repeating unitrepresented by formula (2), Ys in the number m, contained in therepeating structure, are independent of each other.

This is described below by referring to, for example, the followingstructural formula (5) showing the case where X is derived from1,4-cyclohexanedicarboxylic acid.

wherein each Y independently represents an organic residue derived froma polyhydric alcohol having from 2 to 20 carbon atoms and containingfrom 2 to 6 hydroxyl groups, and m represents 0 or an integer of 1 ormore.

In the structural formula (5), the Ys in the number m may all be organicresidues derived from different polyhydric alcohols (that is, organicresidues are derived one by one from m kinds of polyhydric alcohols) orall may be organic residues derived from the same kind of polyhydricalcohol (that is, organic residues in the number m are derived from onekind of a polyhydric alcohol). A mixed structure may also be formed,where out of the Ys in the number m, some are organic residues derivedfrom the same kind of polyhydric alcohol and some others are organicresidues derived from different kinds of polyhydric alcohols.Furthermore, the mixed structure may be completely random throughout thestructure or, in the mixed structure, a part may be repeated.

In the case where a part or all of the Ys are organic residues derivedfrom a polyhydric alcohol having 3 or more hydroxyl groups, a part orall of the Ys can further have, by the ester bonding, a branchedstructure having a terminal group of formula (1) and a repeating unit offormula (2). More specifically, for example, when an organic residuederived from trimethylolpropane as one example of a trihydric alcohol ispresent in the Ys, the alicyclic allyl ester compound having a terminalstructure of formula (I) and a repeating unit of formula (2) of thepresent invention (I) may have a partial structure represented by thefollowing structural formula (6):

wherein each X independently represents an organic residue derived froma polyhydric carboxylic acid having an alicyclic structure.

Of course, even when apart or all of the Ys is an organic residuederived from a polyhydric alcohol having 3 or more hydroxyl groups, Ymay not have a branched structure at all.

The hydroxyl groups may be retained as such. In particular, in the casewhere a part of all of the Ys is an organic residue derived from apolyhydric alcohol having 3 or more hydroxyl groups and having nobranched structure, the hydroxyl group in the moiety having no branchedstructure may be retained as such, but the alicyclic (meth)allyl estercompound of the present invention (II) may also include such a compound.

In formula (2), each Y independently represents one or more kind oforganic residue derived from a polyhydric alcohol having from 2 to 20carbon atoms and containing from 2 to 6 hydroxyl groups. Examples of the“polyhydric alcohol having from 2 to 20 carbon atoms and containing from2 to 6 hydroxyl groups” as used herein include the following compounds.

Specific examples of dihydric alcohols include ethylene glycol,propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol,neopentyl glycol, hexamethylene glycol and 1,4-cyclohexanedimethanol.

Specific examples of trihydric or greater polyhydric alcohols includeglycerin, trimethylolpropane, trimethylolethane, penthaerythritol,dipentaerythritol and sorbitol. In addition, dihydric alcoholscontaining an ether group in the main chain may be used, such asdiethylene glycol, dipropylene glycol, triethylene glycol andpolyethylene glycol. A mixture of two or more of these polyhydricalcohols may also be used. Needless to say, the present invention is notlimited to these specific examples.

Among these polyhydric saturated alcohols, in view of the flowability ofthe allicyclic allyl ester compound having a terminal structure offormula (1) and a repeating unit of formula (12), preferred arepropylene glycol, neopentyl glycol, 1,4-butanediol and diethyleneglycol, and more preferred are propylene glycol and 1,4-butanediol.

The repeating number of the group represented by formula (2) is notparticularly limited. A mixture of materials having various repeatingnumbers may also be used. Furthermore, a material having a repeatingnumber of 0 may be used in combination with a material where therepeating number is an integer of 1 or more. However, use of only acompound where the repeating number is 0 is not preferred from thestandpoint of achieving the object of the present invention.

Usually, the repeating number of the group represented by formula (2) asa repeating unit of the alicyclic allyl ester compound of the presentinvention (II) is preferably an integer of 1 to 50. If an alicyclicallyl ester compound comprising only a compound having a repeatingnumber in excess of 50 is used for a plastic lens composition, the allylgroup concentration decreases and this may cause adverse effects, forexample, at the curing, the curing may be retarded or a part of thecompound may remain uncured to reduce the physical properties such asmechanical properties of the cured product. In all compounds containedin the alicyclic allyl ester compound, the repeating number ispreferably an integer from 1 to 50, more preferably from 1 to 30, stillmore preferably from 1 to 10.

Depending on the production conditions, the alicyclic (meth)allyl estermonomer as a starting material remains in the alicyclic allyl estercompound having a terminal structure of formula (1) and a repeating unitof formula (2), and this monomer may be used as it is in the plasticlens material. However, if the alicyclic (meth)allyl ester monomer as astarting material is present in 70% by mass or more based on the totalamount of the alicyclic allyl ester compound of the present invention(II), when this compound is blended with the compound of formula (3) toprepare a plastic lens composition which is described later, dyeingspecks may be disadvantageously generated or the mold may be damaged atthe time of separating the cured product from the glass mold.

The plastic lens compositions of the present invention (III) and thepresent invention (IV) are described below. The present invention (III)is a plastic lens composition comprising an alicyclic (meth)allyl estercompound of the present invention (II).

The present invention (IV) is a plastic lens composition comprising atleast one radical polymerization initiator in an amount of 0.1 to 10parts by mass per 100 parts by mass of the entire curable componentcontained in the plastic lens composition.

The compound represented by formula (7) which may be contained in theplastic lens composition of the present invention (III) or the presentinvention (IV) can be synthesized by a conventional method. Examplesthereof include a method of transesterifying a di(meth)allyl carbonateand a polyhydric alcohol in the presence of a catalyst (see, JapaneseExamined Patent Publication No. 3-66327, JP-B-3-66327) and a method ofreacting a (meth)allyl alcohol with phosgene and a polyhydric alcoholwhile performing dehydrochlorination (see, U.S. Pat. Nos. 2,370,565 and2,592,058), but the present invention is not limited thereto.

The term “di(meth)allyl carbonate” as used herein means at least onecompound selected from a diallyl carbonate, a dimethallyl carbonate, anallyl methallyl carbonate and a mixture thereof.

wherein Z represents one or more organic residues derived from apolyhydric saturated alcohol having from 2 to 20 carbon atoms andcontaining hydroxyl group in the number of n, n represents an integer of2 to 6, R² represents an allyl group or a methallyl group, provided thateach R² is independent, s represents an integer of 0 to (n−1), t is aninteger of 1 to n, and s+t=n.

In formula (3), Z represents one or more organic residues derived from apolyhydric saturated alcohol having from 2 to 20 carbon atoms andcontaining from 2 to 6 hydroxyl groups. Examples of the “polyhydricsaturated alcohol having from 2 to 20 carbon atoms and containing from 2to 6 hydroxyl groups” as used herein include the following compounds.

Specific examples of dihydric saturated alcohols include ethyleneglycol, propylene glycol, 1,3-propanediol, 1,4-butanediol,1,3-butanediol, neopentyl glycol, hexamethylene glycol and1,4-cyclohexane dimethanol.

Specific examples of trihydric or greater polyhydric saturated alcoholsinclude glycerin, trimethylolpropane, trimethylolethane,penthaerythritol, dipentaerythritol and sorbitol. In addition, dihydricsaturated alcohols containing an ether group in the main chain, such asdiethylene glycol, dipropylene glycol, triethylene glycol orpolyethylene glycol may also be used. A mixture of two or more of thesealcohols may also be used. Needless to say, the present invention is notlimited to these specific examples.

Among these polyhydric saturated alcohols, preferred are ethyleneglycol, propylene glycol, diethylene glycol and dipropylene glycol, morepreferred is diethylene glycol. When diethylene glycol is used as thepolyhydric saturated alcohol, the poly(allyl carbonate) obtained isdiethylene glycol bis(allyl carbonate) and specific examples thereofinclude CR-39, a trade name, produced by PPG, and Nouryset 20, a tradename, produced by Akzo Nobel.

In formula (7), R² represents an allyl group or a methallyl group,provided that each R² is independent. For example, when n is 3, thecompound of formula (7) is a mixture of the compounds represented by thefollowing structural formulae (8) to (10):

In these compounds, for example, in structural formula (8), the threeR²s may all be an allyl group or may all be a methallyl group. It isalso possible that two R²s are an allyl group and one R² is a methallylgroup or that one R² is an allyl group and two R²s are a methallylgroup. Of course, the same applies to two R²s in structural formula (9)and the R² in structural formula (10).

In formula (7), Z is one or more organic residues derived from apolyhydric saturated alcohol having from 2 to 20 carbon atoms andcontaining from 2 to 6 hydroxyl groups. If a plastic lens composition isproduced using a compound having an organic residue as Z derived from apolyhydric saturated alcohol where the number of hydroxyl groups is aninteger in excess of 6, the plastic lens obtained by curing thecomposition may be disadvantageously deteriorated in impact resistance.Also, if a plastic resin composition is produced using a compound havingan organic residue as Z derived from a saturated alcohol where thenumber of hydroxyl groups is an integer of less than 2 (that is, 1), theplastic lens obtained by the curing is extremely reduced in heatresistance and solvent resistance and this is not preferred.

Assuming that the number of hydroxyl groups in Z is n, s is any oneinteger between 0 and n−1, t is any one integer between 1 and n, ands+t=n. In formula (7), t may be sufficient if it is an integer of atleast 1 or more but in view of the physical properties of the finalplastic lens, as many hydroxyl groups as possible are preferablysubstituted by carbonate groups. Although it may vary depending on thecompositional ratio of respective compounds where t is less than n, thecompound where t is n preferably accounts for 80% by mass or more, morepreferably 90% by mass or more, in the compound represented by formula(7).

The amount of the alicyclic allyl ester compound of the presentinvention (II) blended is preferably from 0.1 to 20% by mass, morepreferably from 1 to 15% by mass, still more preferably from 2 to 10% bymass, based on the entire curable component contained in the plasticlens composition of the present invention (III) or the present invention(IV). If the amount of the compound blended is less than 0.1% by mass,the effect of reducing uneven dyeing may not be brought out, whereas ifthe amount blended exceeds 20% by mass, the profitabilitydisadvantageously decreases.

The term “entire curable component” as used herein means the totalamount of the compound represented by formula (1), the compoundrepresented by formula (2) and a monomer copolymerizable with thecompound represented by formula (1) or the compound represented byformula (2).

The amount of the compound represented by formula (3) is 60 to 99.9% bymass, preferably from 75 to 99% by mass, more preferably from 80 to 98%by mass. If the amount blended is less than 60% by mass, the plasticlens obtained by curing the composition may be deteriorated in themechanical properties and optical properties, whereas if it exceeds99.9% by mass, dyeing failure disadvantageously occurs.

The plastic lens composition of the present invention (III) or thepresent invention (IV) may contain, mainly for the purpose of adjustingthe viscosity of the composition, one or more monomers copolymerizablewith the poly(allyl carbonate) represented by formula (7) or with thealicyclic allyl ester compound having a terminal structure of formula(1) and a repeating unit of formula (2), within the range not exceeding20% by mass based, on the entire curable component contained in theplastic lens composition of the present invention.

Examples of the monomers include monomers having an acryl group, a vinylgroup or an allyl group. Specific examples of the monomer having anacryl group include methyl (meth)acrylate and isobornyl (meth)acrylate;specific examples of the monomer having a vinyl group include vinylacetate and vinyl benzoate; and specific examples of the monomer havingan allyl group include diallyl 1,2-cyclohexane dicarboxylate, diallyl1,3-cyclohexane dicarboxylate and diallyl 1,4-cyclohexane dicarboxylate.Of course, the present invention is not limited to these specificexamples and within the range of not impairing the physical propertiesof the plastic lens obtained by curing, diallyl phthalate, diallylterephthalate, diallyl isophthalate, allyl benzoate and the like mayalso be used.

On taking account of workability in the casting, the viscosity of theplastic lens composition of the present invention (III) or the presentinvention (IV) is generally in the range from 10 to 10,000 mPa·s at 25°C., preferably from 10 to 5,000 mPa·s, more preferably from 10 to 500mPa·s.

The term “viscosity” as used herein means a viscosity measured by arotational viscometer. The rotary viscometer is described in detail inIwanami Rikagaku Jiten (Iwanami Physics and Chemistry Encyclopedia), 3rded., 8th imp. (Jun. 1, 1977).

The amount of the monomer added is 20% by mass or less, preferably 10%by mass or less, and more preferably 5% by mass or less, based on theentire curable component contained in the plastic lens composition ofthe present invention. If the monomer is added in excess of 20% by mass,the physical property values required for the plastic lens obtained bycuring the composition, such as optical property, may bedisadvantageously reduced. An optimal monomer is selected by takingaccount of the kind and the mixing ratio of poly(allyl carbonate) andallyl ester oligomer contained in the plastic lens composition and thephysical property values, such as optical properties, required of theplastic lens obtained by curing.

The plastic lens composition of the present invention (IV) may contain aradical polymerization initiator as a curing agent and this ispreferred.

The radical polymerization initiator which can be added to the plasticlens composition of the present invention (IV) is not particularlylimited and a known radical polymerization initiator may be added aslong as it does not adversely affect the physical property values, suchas optical properties, of the plastic lens obtained by curing thecomposition.

The radical polymerization initiator for use in the present inventionis, however, preferably soluble in other components present in thecomposition to be cured, and preferably generates free radicals at 30 to120° C. Specific examples of the radical polymerization initiator whichcan be added include diisopropylperoxy dicarbonate, dicyclohexylperoxydicarbonate, di-n-propylperoxy dicarbonate, di-sec-butylperoxydicarbonate and tert-butyl perbenzoate, but the present invention is notlimited thereto. In view of the curability, diisopropylperoxydicarbonate is preferred.

The amount of the radical polymerization initiator added is in the rangefrom 0.1 to 10 parts by mass, preferably from 1 to 5 parts by mass,based on the entire curable component contained in the plastic lenscomposition of the present invention. If the amount added is less than0.1 part by mass, the composition may be insufficiently cured, whereasif it exceeds 10 parts by mass, the profitability disadvantageouslydecreases.

The plastic lens composition of the present invention (III) or thepresent invention (IV) may contain additives commonly used for thepurpose of improving the performance of the plastic lens, such as acoloring agent including dye and pigment, an ultraviolet absorbent, amold-releasing agent and an antioxidant.

Examples of the coloring agent include organic pigments such as ananthraquinone type, an azo type, a carbonium type, a quinoline type, aquinoneimine type, an indigoid type and a phthalocyanine type; organicdyes such as an azoic dye and a sulfur dye; and inorganic pigments suchas titanium yellow, yellow iron oxide, zinc yellow, chrome orange,molybdenum red, cobalt violet, cobalt blue, cobalt green, chromic oxide,titanium oxide, zinc sulfide and carbon black.

Examples of the mold-releasing agent include stearic acid, butylstearate, zinc stearate, stearic acid amide, fluorine-containingcompounds and silicon compounds.

Examples of the ultraviolet absorbent include triazoles such as2-(2′-hydroxy-tert-butylphenyl)benzo-triazole, benzophenones such as2,4-dihydroxybenzophenone, salicylates such as 4-tert-butylphenylsalicylate, and hindered amines such asbis-(2,2,6,6-tetramethyl-4-piperidinyl)sebacate.

Examples of the antioxidant include phenols such as2,6-di-tert-butyl-4-methylphenol and tetrakis[methylene-3-(3′,5′-di-tert-butyl-4-hydroxyphenyl)propionate]methane; sulfurs such asdilauryl-3,3′-thiodipropionlate; and phosphorus-containing antioxidantssuch as trisnonylphenylphosphite.

The total amount of the additives added, such as a coloring agentincluding dye and pigment, an ultraviolet absorbent, a mold-releasingagent and an antioxidant, is preferably 1% by mass or less based on theentire curable resin component contained in the plastic lens resincomposition of the present invention.

The plastic lens of the present invention (V) is described below. Thepresent invention (V) is a plastic lens obtained by curing the plasticlens composition of the present invention (III) or the present invention(IV).

The plastic lens of the present invention preferably has a refractiveindex of 1.497 to 1.505 at 25° C. The mold for use in the production ofa plastic lens (refractive index: 1.498 at 25° C.) using the compoundrepresented by formula (7) as a raw material is a mold suitable only forthe production of plastics having the same refractive index. As long asthe same mold is used, a change in the refractive index means a changein the capability of the lens.

For obtaining a plastic lens having the same ability from a compositionfor lenses having a high refractive index, a different mold isnecessary. Accordingly, unless the refractive index of a lens obtainedis limited so as to eliminate the necessity of changing the mold, theimprovement in the properties of a lens attributable to the introductionof the alicyclic allyl ester compound having a terminal structure offormula (1) and a repeating unit of formula (2), the compoundrepresented by formula (7), and the monomer copolymerizable with thealicyclic allyl ester compound having a terminal structure of formula(1) and a repeating unit of formula (2) or with the compound representedby formula (7), may not be achieved. The refractive index at 25° C. ofthe plastic lens of the present invention is preferably from 1.498 to1.505, more preferably from 1.498 to 1.503.

The present invention (VI) is described below. The present invention(VI) is a production process of the plastic lens of the presentinvention (V), comprising curing the plastic lens composition of thepresent invention (III) or the present invention (IV).

In the present invention, the mold-working of the plastic lenscomposition is suitably performed by cast molding. Specific examplesthereof include a method of adding a radical polymerization initiator tothe composition, injecting the mixture through a line into a mold fixedby an elastomer,gasket or a spacer, and curing it under heating in anoven.

The constructive material of the mold used here is a metal or glass. Ingeneral, the mold for plastic lenses must be cleaned after the castmolding and such cleaning is usually performed using a strong alkalisolution or a strong acid. Unlike a metal, glass is scarcely changed bythe cleaning and furthermore, glass can be easily polished and therebyextremely reduced in the surface roughness. From these reasons, glass ispreferably used.

The plastic lens composition of the present invention (III) or thepresent invention (IV) has an alicyclic structure, therefore, therefractive index can be easily approximated to the refractive index1.498 of a plastic lens starting from polyethylene glycol bis(allylcarbonate) which is used for plastic lenses in many cases. This isadvantageous in that the mold or the like conventionally used in themolding needs not be changed but can be used as it is.

The curing temperatures at molding is from about 30 to 120° C.,preferably from 40 to 100° C. On taking account of shrinkage or strainat the curing, the curing temperature is preferably operated to allowthe curing to gradually proceed while elevating the temperature. Thecuring time is generally from 0.5 to 100 hours, preferably from 3 to 50hours, more preferably from 10 to 30 hours.

The method for dyeing the plastic lens of the present invention is notparticularly limited. Any method may be used as long as it is a knowndyeing method for plastic lenses. Among these, a dip dyeing method as aconventionally known ordinary method is preferred. The “dip dyeingmethod” as used herein means a method of dispersing a disperse dyetogether with a surfactant in water to prepare a dye bath and dipping aplastic lens in this dyeing solution under heating, thereby dyeing theplastic lens.

The method for dyeing the plastic lens is not limited to the dip dyeingmethod but other known methods may be used, such as a method ofsublimating an organic pigment and thereby dyeing;a plastic lens (see,Japanese Examined Patent Publication No. 35-1384, JP-B-35-1384) and amethod of sublimating a sublimable dye and thereby dyeing a plastic lens(see, Japanese Examined Patent Publication Nos. 56-159376 and 1-277814,JP-B-56-159376 and JP-B-1-277814). In view of simple operation, the dipdyeing method is most preferred.

The present invention is further illustrated below by referring to thefollowing examples, however, the present invention should not beconstrued as being limited thereto.

The measurement conditions for gas chromatography (hereinafter simplyreferred to as “GC”) and liquid chromatography (hereinafter simplyreferred to as “LC”) employed in the examples are shown below.

GC Conditions

Apparatus used: GC-14B (manufactured by Shimadzu Corp.)

Detector: hydrogen flame ionization detector

Measuring method: internal standard method (internal standard substance:n-butyl acetate)

Injection temperature: 220° C.

Temperature condition: The temperature was kept at 40° C. for 10minutes, thereafter elevated at a rate of 5° C./minute and then kept at220° C. for 10 minutes.

Column used DB-WAX (produced by J & W), inner diameter: 0.25 mm, length:30 m

LC Conditions

Eluent: aqueous 0.1 mass % phosphoric acid solution : acetonitrile=60:40(v/v)

Flow rate: 1 ml/min

Detector: RI detector

Measuring method: internal standard method (internal standard substance:ethyl acetate)

Column used: 2 rolls in series of Shodex ODSpak F-511

Oven temperature: 40° C.

Various physical properties were measured as follows.

1. Refractive Index (n_(D)) and Abbe Number (ν_(D))

A test piece of 9 mm×16 mm×4 mm was prepared and measured on therefractive index (n_(D)) and Abbe number (ν_(D)) at room temperatureusing “Abbe Refractometer 1T” manufactured by Atago. The contact solventused was α-bromonaphthalene.

2. Viscosity

The viscosity was measured at 25° C. using Model B Viscometer (ModelB8U) manufactured by Tokyo Keiki Co., Ltd.

3. Measuring Method of Hazen Color Number

The Hazen color number was measured by the method described in JISK-0071-1.

4. Barcol Hardness

The Barcol hardness was measured using Model 934-1 according to JISK-6911.

5. Dyeing Method and Evaluation of Uneven Dyeing

To a 1 l beaker, 0.8 g of Sumikaron Blue E-FBL (produced by SumitomoChemical Co., Ltd.) and 0.5 L of water were added and dissolved withstirring. The resulting solution was heated at 80° C. in a water bathand into this disperse dye solution, cured plastic lens samples eachfixed to a holder so as not to overlap one on another were dipped at 8°C. for 10 minutes. Thereafter, the samples were taken out, thoroughlywashed with water and then hot-air dried in an oven at 30° C.

The thus-obtained dyed plastic lens samples were observed with an eyeand those failed in having a uniformly dyed appearance and revealed tohave uneven dyeing were rated “defective”. In the evaluation, 30 curedsamples in total were used and the number of “defective” samples wascounted.

EXAMPLE 1

Into a 300 ml three-neck flask with a thermometer and a rectifyingtower, 100 g of dimethyl 1,4-cyclohexanedicarboxylate (hereinaftersimply referred to as “CHDM”), 120 g of allyl alcohol, 0.25 g of calciumhydroxide and 0.05 g of potassium acetate were charged and reacted underheating in an oil bath adjusted to 120° C. The reaction was performedfor 10 hours while distilling out methanol produced with the progress ofthe reaction from the rectifying tower. After the completion ofreaction, it was confirmed by GC analysis that 98.8% of diallyl1,4-cyclohexanedicarboxylate was produced based on CHDM. Thereafter, theallyl alcohol remaining in the system was distilled off under reducedpressure and the catalyst was removed by filtration. The filtrate was analmost colorless transparent liquid and the Hazen color number thereofwas 5.

This filtrate was directly distilled under reduced pressure to obtain121 g of colorless and transparent diallyl 1,4-cyclohexanedicarboxylatehaving a boiling point of 140 to 142° C./26.6 Pa (yield: 95%). Thethus-obtained diallyl 1,4-cyclohexanedicarboxylate was designated as“Sample A”.

EXAMPLE 2

A reaction was initiated under the same conditions as in Example 1except for,changing 0.25 g of calcium hydroxide to 0.25 g of calciumoxide. The reaction time and the yield by GC are shown in Table 1.

EXAMPLE 3

A reaction was initiated under the same conditions as in Example 1except for changing 0.25 g of calcium hydroxide to 0.25 g of magnesiumhydroxide. The reaction time and the yield by GC are shown in Table 1.

EXAMPLE 4

A reaction was initiated under the same conditions as in Example 1except for changing 0.25 g of barium hydroxide to 0.25 g of calciumoxide. The reaction time and the yield by GC are shown in Table 1.

TABLE 1 Yield by GC Reaction Time (based on CHDM) Example 1 10 hours98.8% Example 2 20 hours 93.2% Example 3 34 hours 67.9% Example 4 20hours 91.4%

EXAMPLE 5

A reaction was initiated under the same conditions as in Example 1except for changing 0.05 g of potassium acetate to 0.05 g of sodiumacetate. The reaction time and the yield by GC are shown in Table 2.

EXAMPLE 6

A reaction was initiated under the same conditions as in Example 1except for changing 0.05 g of potassium acetate to 0.05 g oftripotassium phosphate. The reaction time and the yield by GC are shownin Table 2.

EXAMPLE 7

A reaction was initiated under the same conditions as in Example 1except for changing 0.05 g of potassium acetate to 0.05 g of sodiumhydrogen carbonate. The reaction time and the yield by GC are shown inTable 2.

EXAMPLE 8

A reaction was initiated under the same conditions as in Example 1except for changing 0.05 g of potassium acetate to 0.05 g of potassiumsulfate. The reaction time and the yield by GC are shown in Table 2.

EXAMPLE 9

A reaction was initiated under the same conditions as in Example 1except for changing 0.05 g of potassium acetate to 0.05 g of potassiumchloride. The reaction time and the yield by GC are shown in Table 2.

EXAMPLE 10

A reaction was initiated under the same conditions as in Example 1except for changing 0.05 g of potassium acetate to 0.05 g of potassiumcarbonate. The reaction time and the yield by GC are shown in Table 2.

EXAMPLE 11

A reaction was initiated under the same conditions as in Example 1except for changing 0.05 g of potassium acetate to 0.05 g of lithiumcarbonate. The reaction time and the yield by GC are shown in Table 2.

EXAMPLE 12

A reaction was initiated under the same conditions as in Example 1except for changing 0.05 g of potassium acetate to 0.05 g of sodiumcarbonate. The reaction time and the yield by GC are shown in Table 2.

EXAMPLE 13

A reaction was initiated under the same conditions as in Example 1except for changing 0.05 g of potassium acetate to 0.05 g of rubidiumcarbonate. The reaction time and the yield by GC are shown in Table 2.

TABLE 2 Yield by GC Catalyst Reaction Time (based on CHDM) Example 5 14hours 93.6% Example 6 11 hours 94.6% Example 7 13 hours 91.9% Example 816 hours 95.1% Example 9 17 hours 94.7% Example 10 16 hours 97.2%Example 11 38 hours 91.3% Example 12 25 hours 94.9% Example 13 15 hours96.8%

EXAMPLE 14

Into a 300 ml three-neck flask with a thermometer and a rectifyingtower, 100 g of CHDM, 149 g of methallyl alcohol, 0.25 g of calciumhydroxide and 0.05 g of potassium acetate were charged and reacted underheating in an oil bath adjusted to 120° C. The reaction was performedfor 15 hours while distilling out methanol, produced with the progressof the reaction, from the rectifying tower. After the completion ofreaction, it was confirmed by GC analysis that 94.0% of dimethallyl1,4-cyclohexanedicarboxylate was produced based on CHDM.

EXAMPLE 15

A reaction was initiated under the same conditions as in Example 1except for using 100 g of dimethyl 1,3-cyclohexanedicarboxylate in placeof 100 g of CHDM. The reaction time and the yield by GC are shown inTable 3.

EXAMPLE 16

A reaction was initiated under the same conditions as in Example 1except for using 100 g of dimethyl 1,2-cyclohexanedicarboxylate in placeof 100 g of CHDM. The reaction time and the yield by GC are shown inTable 3.

EXAMPLE 17

A reaction was initiated under the same conditions as in Example 1except for using 129 g of trimethyl 1,2,4-cyclohexanetricarboxylate inplace of 100 g of CHDM. The reaction time and the yield by GC are shownin Table 3.

EXAMPLE 18

A reaction was initiated under the same conditions as in Example 1except for using 158 g of tetramethyl1,2,4,5-cyclohexanetetracarboxylate in place of 100 g of CHDM andchanging the amount of allyl alcohol used from 120 g to 240 g. Thereaction time and the yield by GC are shown in Table 3.

EXAMPLE 19

A reaction was initiated under the same conditions as in Example 1except for using 114 g of diethyl 1,4-cyclohexanedicarboxylate in placeof 100 g of CHDM. The reaction time and the yield, by GC are shown inTable 3.

EXAMPLE 20

A reaction was initiated under the same conditions as in Example 1except for using 128 g of diisopropyl 1,4-cyclohexanedicarboxylate inplace of 100 g of CHDM. The reaction time and the yield by GC are shownin Table 3.

TABLE 3 Yield by GC or LC Reaction Time (based on raw materials) Example14 15 hours 94.0% (GC) Example 15 10 hours 97.1% (GC) Example 16 20hours 91.1% (GC) Example 17 30 hours 92.9% (LC) Example 18 20 hours87.1% (LC) Example 19 15 hours 96.9% (GC) Example 20 25 hours 93.4% (GC)

EXAMPLE 21

A reaction was initiated under the same conditions as in Example 1except for using 2.0 g of calcium hydroxide in place of 0.25 g ofcalcium hydroxide and 0.05 g of potassium acetate. The reaction time andthe yield by GC are shown in Table 4.

EXAMPLE 22

A reaction was initiated under the same conditions as in Example 1except for using 1.0 g of potassium carbonate in place of 0.25 g ofcalcium hydroxide and 0.05 g of potassium acetate. The reaction time andthe yield by GC are shown in Table 4.

EXAMPLE 23

A reaction was initiated under the same conditions as in Example 1except for using 2.0 g of tetraisopropyl titanate in place of 0.25 g ofcalcium hydroxide and 0.05 g of potassium acetate. The reaction time andthe yield by GC are shown in Table 4.

EXAMPLE 24

A reaction was initiated under the same conditions as in Example 1except for using 2.0 g of sodium methoxide in place of 0.25 g of calciumhydroxide and 0.05 g of potassium acetate. The reaction time and theyield by GC are shown in Table 4.

EXAMPLE 25

A reaction was initiated under the same conditions as in Example 1except that 2.0 g of calcium hydroxide was used in place of 0.25 g ofcalcium hydroxide and 0.05 g of potassium acetate, 2.0, g of dibutyltinoxide was used, the pressure was changed from atmospheric pressure to0.6 MPa (gauge pressure) and the oil bath temperature was changed from120° C. to 170° C. The reaction time and the yield by GC are shown inTable 4.

EXAMPLE 26

A reaction was initiated under the same conditions as in Example 1except for using 2.0 g of zinc acetylacetonate in place of 0.25 g ofcalcium hydroxide and 0.05 g of potassium acetate. The reaction time andthe yield by GC are shown in Table 4.

EXAMPLE 27

A reaction was initiated under the same conditions as in Example 1except for using 2.0 g of hafnium acetylacetonate in place of 0.25 g ofcalcium hydroxide and 0.05 g of potassium acetate. The reaction time andthe yield by GC are shown in Table 4.

EXAMPLE 28

A reaction was initiated under the same conditions as in Example 1except for using 2.0 g of 1,4-diazabicyclo[2.2.2]octane in place of 0.25g of calcium hydroxide and 0.05 g of potassium acetate. The reactiontime and the yield by GC are shown in Table 4.

TABLE 4 Reaction Yield by GC Time (based on DMI) Remarks Example 21 18hours 95.8% not colored Example 22 12 hours 96.2% colored Example 23 20hours 94.7% slightly colored Example 24 18 hours 55.7% colored Example25 25 hours 95.9% not colored Example 26 30 hours 40.7% slightly coloredExample 27 25 hours 90.5% slightly colored Example 28 15 hours 95.0%slightly colored

COMPARATIVE EXAMPLE 1

Into the same reaction apparatus as in Example 1, 100 g of1,4-cyclohexanecarboxylic acid, 120 g of allyl alcohol, 100 g of benzeneand 1 g of sulfuric acid were charged and reacted under heating in anoil bath adjusted to 120° C. At the time when 23 g of water wasprecipitated, the reaction was terminated and the reaction product wasanalyzed by GC and found to contain 5% of diallyl ether (based ondiallyl 1,4-cyclohexanecarboxylate). The solution was transferred to a 1l separating funnel, 50 g of an aqueous 1% sodium hydroxide solution wascharged there-into, a liquid separation operation was performed and theaqueous phase was removed. The same operation was again repeated, andthen benzene and allyl alcohol in the oil phase was distilled off underreduced pressure by an evaporator. Thereafter, the components which werenot distilled off by the evaporator were directly distilled underreduced pressure to obtain 177.7 g of diallyl1,4-cyclohexanedicarboxylate as a slightly yellow transparent liquid(yield: 94%). The sulfur content of this liquid was analyzed by achlorine-sulfur analyzer Model TSX-10 (manufactured by MitsubishiKagaku) and confirmed to be 30 ppm by mass. This diallyl1,4-cyclohexnedicarboxylate was designated as “Sample B”. Evaluation ofStorage Stability of Sample A and Sample B

Samples A and B immediately after the production and Samples A and Bstored at 25° C. for 1 year after the production were measured on theHazen color number. The results are shown in Table 5 below.

TABLE 5 Hazen Color Number Immediately after Stored at 25° C. for 1 YearSample Used Production after Production Sample A less than 5 less than 5Sample B 5 15

EXAMPLE 29 Production of Alicyclic Allyl Ester Compound

Into a 1 l three-neck flask with a distilling unit, 120.0 g of Sample A,24.1 g of propylene glycol and 0.12 g of dibutyltin oxide were charged.Under a nitrogen stream, the system was heated to 180° C. and the allylalcohol generated was distilled off. When about 27.7 g of allyl alcoholwas distilled off, the pressure inside the reaction system was reducedto 1.33 kPa to increase the distillation rate of allyl alcohol. After atheoretical amount of allyl alcohol was distilled off, the reactionsystem was heated for another one hour and then kept at 180° C. and 0.13kPa for one hour. Thereafter, the reactor was cooled, then, 107.5 g ofan allyl ester compound was obtained (hereinafter referred to as “SampleC”).

The thus-obtained sample C was analyzed by gas chromatography (GC-14B,manufactured by Shimadzu Corp., using a hydrogen flame ionizationdetector and a column OV-17 of 0.5 m under a constant temperaturecondition of 160° C.) and found to contain 13% by mass of diallyl1,4-cyclohexanedicarboxylate.

FIG. 1 shows the 400 MHz ¹H-NMR spectrum of this sample.

COMPARATIVE EXAMPLE 2 Production of Alicyclic Allyl Ester Compound

Into a 1 l three-neck flask with a distilling unit, 120.0 g of Sample B,24.1 g of propylene glycol and 0.12 g of dibutyltin oxide were charged.Under nitrogen stream, the system was heated at 180° C. and the allylalcohol generated was distilled off. When about 27.7 g of allyl alcoholwas distilled off, the pressure inside the reaction system was reducedto 1.33 kPa to increase the distillation rate of the allyl alcohol.After a theoretical amount of allyl alcohol was distilled off, thereaction system was heated for another one hour and kept at 180° C. and0.13 kPa for one hour. Thereafter, the reactor was cooled, then, 107.5 gof an allyl ester compound was obtained (hereinafter referred to as“Sample D”).

The thus-obtained sample D was analyzed by gas chromatography (GC-14B:manufactured by Shimadzu Corp., using a hydrogen flame ionizationdetector and a column OV-17 of 0.5 m under a constant temperaturecondition of 160° C.) and found to contain 12% by mass of diallyl1,4-cyclohexanedicarboxylate.

FIG. 2 shows the 400 MHz ¹H-NMR spectrum of this sample.

EXAMPLE 30 Measurement of Refractive Index, Abbe Number and BarcolHardness of Lens, and Evaluation of Dyeing Speck

As shown in Table 6, 95.0 parts by mass of diethylene glycol bis(allylcarbonate) (CR-39, a trade name, produced by PPG), 5 parts by mass ofSample C and 3 parts by mass of diisopropylperoxy dicarbonate (IPP) wereblended and mixed with stirring to form a completely homogeneoussolution composition. The viscosity at this time was measured.Thereafter, the vessel containing this solution was placed in adesiccator capable of depressurization and the pressure was reduced by avacuum pump for about 15 minutes to deaerate gases in the solution. Theresulting solution composition was injected by a syringe into a moldfabricated from a glass-made mold for ophthalmic plastic lenses and aresin-made gasket, while taking care to prevent intermixing of gas, andthen cured in an oven according to a temperature program such thatheating at 40° C. for 7 hours, heating at from 40° C. to 60° C. for 10hours, heating at from 60° C. to 80° C. for 3 hours, heating at 80° C.for 1 hour and heating at 85° C. for 2 hours occurred.

The thus-obtained lens was measured for refractive index, Abbe numberand Barcol hardness, and evaluated on uneven dyeing. The results thereofare shown in Table 6.

TABLE 6 Comparative Comparative Example 30 Example 3 Example 4 BlendNouryset 200 95.0 95.0 100.0 (parts by Sample C 5.0 mass) Sample D 5.0(25° C.) (mPa · s) 28 28 25 Initiator IPP (parts by 3 3 3 mass) PhysicalRefractive 1.503 1.503 1.501 Properties index (n_(D)) Abbe 55 55 58number (ν_(D)) Barcol 31 31 33 hardness Uneven 1 1 10 dyeing (number)

COMPARATIVE EXAMPLES 3 and 4

Compositions were prepared to have a blend shown in Table 6 and in thesame manner as in Example 1, the viscosity was measured and then thelens was measured for the refractive index, Abbe number and Barcolhardness and evaluated on uneven dyeing. The results are shown in Table6.

INDUSTRIAL APPLICABILITY

According to the present invention, an alkyl ester of a polybasic acidhaving an alicyclic structure, which has been heretofore not used as astarting material of a (meth)allyl ester of a polybasic acid having analicyclic structure, and a (meth)allyl alcohol are used and reacted inthe presence of a transesterification catalyst to produce acorresponding alicyclic (meth)allyl ester monomer, whereby an industrialproduction process can be provided at a low cost with out producing anyby-products such as diallyl ether and the product can have excellentlong-term storage stability. The alicyclic (meth)allyl ester compound ofthe present invention produced from the alicyclic (meth)allyl estermonomer obtained by the above-described process and a polyhydric alcoholcan provide a plastic lens having good dyeability by using it incombination with a poly(allyl carbonate) resin.

What is claimed is:
 1. A process for producing an alicyclic (meth)allylester monomer, comprising reacting a polyvalent alkyl ester of apolybasic acid having an alicyclic structure with an allyl alcoholand/or a methallyl alcohol in the presence of a transesterificationcatalyst.
 2. A process as claimed in claim 1, wherein thetransesterification catalyst is at least one compound selected from thegroup consisting of combinations of alkali metal salts of organic acidsand/or inorganic acids with hydroxides and/or oxides of alkaline earthmetals, organic metal compounds, tertiary amines, alkali metal saltsand/or alkaline earth metal salts of carbonic acid, and alkylalkoxidesof alkali metals.
 3. A process for producing an alicyclic (meth)allylester compound, comprising transesterifying an alicyclic (meth)allylester monomer produced by a process as set forth in claim 1 or 2 with apolyhydric alcohol in the presence of la catalyst, said alicyclic(meth)allyl ester compound having a terminal structure of the followingformula (1) and a repeating unit of the following formula (2),

wherein each R¹ independently represents an allyl group or a methallylgroup, each X independently represents an organic residue derived from apolyvalent carboxylic acid having an alicyclic structure, and each Yindependently represents an organic residue derived from a polyhydricalcohol having from 2 to 20 carbon atoms and containing from 2 to 6hydroxyl groups, provided that by the ester bonding, X may have abranched structure having a terminal group of formula (1) and arepeating unit of formula (2) or may have R¹, and that, by the esterbonding, Y may have a branched structure having a terminal group offormula (1) and a repeating unit of formula (2)).